EP1599878B1 - Optical recording materials having high storage density - Google Patents

Optical recording materials having high storage density Download PDF

Info

Publication number
EP1599878B1
EP1599878B1 EP04713552A EP04713552A EP1599878B1 EP 1599878 B1 EP1599878 B1 EP 1599878B1 EP 04713552 A EP04713552 A EP 04713552A EP 04713552 A EP04713552 A EP 04713552A EP 1599878 B1 EP1599878 B1 EP 1599878B1
Authority
EP
European Patent Office
Prior art keywords
substituted
unsubstituted
alkyl
sub
radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP04713552A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1599878A1 (en
Inventor
Urs Lehmann
Peter Sutter
Beat Schmidhalter
Jean-Luc Budry
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Publication of EP1599878A1 publication Critical patent/EP1599878A1/en
Application granted granted Critical
Publication of EP1599878B1 publication Critical patent/EP1599878B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
    • G11B7/2492—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds neutral compounds
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B2007/25705—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G11B2007/25706—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials containing transition metal elements (Zn, Fe, Co, Ni, Pt)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B2007/25705—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G11B2007/2571—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials containing group 14 elements except carbon (Si, Ge, Sn, Pb)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B2007/25705—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G11B2007/25713—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials containing nitrogen
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B2007/25705—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G11B2007/25715—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials containing oxygen
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B2007/25705—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G11B2007/25716—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials containing sulfur
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/247—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes
    • G11B7/2472—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes cyanine
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/247—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes
    • G11B7/2475—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes merocyanine
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/247—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes
    • G11B7/2478—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes oxonol
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
    • G11B7/2495—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds as anions
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2531—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising glass
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
    • G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
    • G11B7/2535—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polyesters, e.g. PET, PETG or PEN
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B7/2572—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of organic materials
    • G11B7/2575—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of organic materials resins

Definitions

  • the invention relates to new optical recording materials that have excellent recording and playback quality especially at a wavelength of 350-500 nm. Recording and playback can be effected very advantageously with high sensitivity at the same wavelength, and the storage density that is achievable is significantly higher than in the case of known materials.
  • the materials according to the invention have very good storage properties before and after recording, even under especially harsh conditions, such as exposure to sunlight or fluorescent lighting, heat and/or high humidity.
  • their manufacture is simple and readily reproducible using customary coating processes, such as spin-coating.
  • WO 02/082438 discloses the use of ionic salts, including those with metal complex anions, for optical recording materials. Those colorants are always substituted by alkyl, alkenyl, aryl or heteroaryl at the nitrogen atom. Their optical properties do not, however, fully satisfy increased demands. In particular, the refractive index as well as the absorption and the steepness of the absorption band on its long wavelength flank in the solid still leave something to be desired.
  • JP-A-11/34500, JP-A-19/92479 and EP-A-0 903 733 disclose metal and boron complexes of colorants of formulae and which can be used at from 520 to 690 nm for optical recording materials such as CD-R or DVD-R.
  • the optical properties, especially the spectral properties in or near the UV range that are necessary for the highest possible storage densities, and the information density per unit surface area are not able to satisfy the highest demands as desired.
  • the information density per unit surface area is far lower than is desirable.
  • J. Org. Chem. 67 /16, 5753-5772 [2002] describes the synthesis of a number of bis( o -azaheteroaryl)methanes and their coordination properties with respect to divalent transition metals, heteroaryl being 1,3-azol-2-yl, 1,3-benzazol-2-yl and azinyl and the transition metals being Zn, Cu, Co, Ni, Hg and Pd.
  • the aim of the invention is an optical recording medium having high information density, sensitivity and data reliability.
  • a recording medium should be robust, durable and easy to use. Furthermore, it should be inexpensive to manufacture as a mass-produced product and should require equipment that is as small and inexpensive as possible.
  • R 5 When R 5 forms a bridge with R 6 , R 5 may not at the same time form a bridge with R 13 or R 14 .
  • acidic groups such as carboxy, sulfo, sulfato and phosphato
  • a salt for example an alkali metal, alkaline earth metal, ammonium or phosphonium salt, such as Li + , Na + , K + , Mg 2+ , Ca 2+ , Cu 2+ , Ni 2+ , Fe 2+ , Co 2+ , Zn 2+ , Sn 2+ , La 3+ , ammonium, methylammonium, ethylammonium, isopropylammonium, TMPrimene 81-R, TMRosin Amine D, pentadecylammonium, TMPrimene JM-T, dicyclohexylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltrimethylammonium, benzyltrieth
  • Halogen is chlorine, bromine, fluorine or iodine, preferably fluorine or chlorine, especially fluorine on alkyl (for example trifluoromethyl, ⁇ , ⁇ , ⁇ -tritluoroethyl or perfluorinated alkyl groups, such as heptafluoropropyl) and chlorine on aryl, heteroaryl or on the aryl moiety of aralkyl or on the heteroaryl moiety of heteroaralkyl.
  • alkyl for example trifluoromethyl, ⁇ , ⁇ , ⁇ -tritluoroethyl or perfluorinated alkyl groups, such as heptafluoropropyl
  • chlorine on aryl, heteroaryl or on the aryl moiety of aralkyl or on the heteroaryl moiety of heteroaralkyl for example trifluoromethyl, ⁇ , ⁇ , ⁇ -tritluoroethyl or perfluorinated alkyl groups, such as
  • Alkyl, cycloalkyl, alkenyl or cycloalkenyl can be straight-chain or branched, or monocyclic or polycyclic.
  • Alkyl is, for example, methyl, straight-chain C 2 -C 24 alkyl or preferably branched C 3 -C 24 alkyl.
  • Alkenyl is, for example, straight-chain C 2 -C 20 alkenyl or preferably branched C 3 -C 24 alkenyl.
  • the invention therefore relates especially also to compounds of formula (I) containing branched C 3 -C 24 alkyl or branched C 3 -C 24 alkenyl, and also to optical recording materials comprising such compounds.
  • C 1 -C 24 Alkyl is therefore, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, heneicosyl, docosyl or tetracosyl.
  • Cycloalkyl is, for example, cydopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1-adamantyl or 2-adamantyl.
  • C 2 -C 20 Alkenyl and C 3 -C 20 cycloalkenyl are C 2 -C 20 alkyl and C 3 -C 20 cycloalkyl that is mono- or poly-unsaturated, wherein two or more double bonds may be isolated or conjugated, for example vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1- p -menthen-8-yl, 4(10)-thuj
  • C 7 -C 12 Aralkyl is, for example, benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, 9-fluorenyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenyl-butyl or ⁇ -phenyl-hexyl.
  • C 7 -C 12 aralkyl is substituted, both the alkyl moiety and the aryl moiety of the aralkyl group can be substituted, the latter alternative being preferred.
  • C 6 -C 12 Aryl is, for example, phenyl, naphthyl, biphenylyl or 2-fluorenyl.
  • C 4 -C 12 Heteroaryl is an unsaturated or aromatic radical having 4 n+2 conjugated ⁇ -electrons, for example 2-thienyl, 2-furyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl or any other ring system consisting of thiophene, furan, pyridine, thiazole, oxazole, imidazole, isothiazole, triazole, pyridine and benzene rings and unsubstituted or substituted by from 1 to 6 ethyl, methyl, ethylene and/or methylene substituents, for example benzotriazolyl, and in the case of N-heterocycles where applicable also those in the form of their N-oxides.
  • 2-thienyl 2-furyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, is
  • C 5 -C 12 Heteroaralkyl is, for example, C 1 -C 8 alkyl substituted by C 4 -C 11 heteroaryl.
  • aryl and aralkyl can also be aromatic groups bonded to a metal, for example in the form of metallocenes of transition metals known per se, more especially
  • the transition metal M 1 is preferably in the form of a doubly positively charged cation, for example Co 2+ , Cu 2+ , Ni 2+ , Pd 2+ or Zn 2+ , especially Co 2+ , Cu 2+ or Ni 2+ .
  • the compound of formula (I) may also be a cation which has been neutralised with an inorganic, organic or organometallic anion, for example when one or more ammonium groups are present or when the transition metal has one or more excess positive charges, such as in Co 3+ .
  • the inorganic, organic or organometallic anion may be, for example, the anion of a mineral acid, of the conjugated base of an organic acid (for example an alcoholate, phenolate, carboxylate, sulfonate or phosphonate) or an organometallic complex anion, for example fluoride, chloride, bromide, iodide, perchlorate, periodate, nitrate, hydrogen carbonate, 1 ⁇ 2 carbonate, 1 ⁇ 2 sulfate, C 1 -C 4 alkyl sulfate, hydrogen sulfate, 1/3 phosphate, 1 ⁇ 2 hydrogen phosphate, dihydrogen phosphate, 1 ⁇ 2 C 1 -C 4 alkanephosphonate, C 1 -C 4 alkane-C 1 -C 12 alkylphosphonate, di-C 1 -C 4 alkylphosphinate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, a
  • 1 x of an inorganic, organic or organometallic anion having x negative charges is a multiply charged anion which neutralises several singly charged cations or a cation having x charges, as the case may be.
  • Phenolates or carboxylates are, for example, of formula (wherein R 29 , R 30 and R 31 are each independently of the others hydrogen, R 18 , or C 6 -C 12 aryl, C 4 -C 12 heteroaryl, C 7 -C 12 aralkyl or C 5 -C 12 heteroaralkyl each unsubstituted or substituted by one or more, where applicable identical or different, radicals R 18, for example anions of C 1 -C 12 alkylated, especially tert-C 4 -C 8 alkylated, phenols and benzoic acids, such as
  • a 1 , A 2 and A 3 are each independently of the others O, S or N(R 12 ) and/or Q 1 and Q 2 are C(R 15 ) or N;
  • G 1 and G 2 are each independently of the other or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 14 are each independently of the others hydrogen, R 18 , or C 6 -C 12 aryl or C 7 -C 12 aralkyl each unsubstituted or substituted by one or more, where applicable identical or different, radicals R 18 ;
  • R 9 , R 12 and R 13 are each independently of the others unsubstituted or R 17 -substituted C 1 -C 8 alkyl;
  • R 12 is C 1 -C 24 alkyl, C 1 -C 4 alkyl-[O-C 1 -C 4 alkylene] m or C 1 -C 4 alkyl-[NH-C 1 -C 4 alkylene] m , each of which is unsubstituted or substituted by one or more, where applicable identical or different, radicals R 17 , or C 6 -C 12 aryl unsubstituted or substituted by one or more, where applicable identical or different, radicals R 18 ;
  • R 15 is hydrogen, cyano, COO-R 25 or C 1 -C 12 alkyl;
  • R 17 is halogen, hydroxy, O-R 25 , cyano, COO-R 25 or carboxy; and
  • the recording layer advantageously comprises a compound of formula (I) or a mixture of such compounds as main component, for example at least 30 % by weight, preferably at least 60 % by weight, especially at least 80 % by weight
  • Further customary constituents are possible, for example other chromophores (for example those disclosed in WO 01/75873, or others having an absorption maximum at from 300 to 1000 nm), stabilisers, 1 O 2 -, triplet- or luminescence-quenchers, melting-point reducers, decomposition accelerators or any other additives that have already been described in optical recording media.
  • stabilisers or fluoresence-quenchers are added if desired.
  • the amount of such chromophores should preferably be small, so that the absorption thereof at the wavelength of the inversion point of the longest-wavelength flank of the absorption of the entire solid layer is a fraction of the absorption of the pure compound of formula (I) in the entire solid layer at the same wavelength, advantageously at most 1/3, preferably at most 1/5, especially at most 1/10.
  • the absorption maximum is preferably higher than 425 nm, especially higher than 500 nm.
  • Stabilisers, 1 O 2 -, triplet- or luminescence-quenchers are, for example, metal complexes of N- or S-containing enolates, phenolates, bisphenolates, thiolates or bisthiolates or of azo, azomethine or formazan dyes, such as bis(4-dimethylaminodithiobenzil)nickel [CAS N° 38465-55-3], ®Irgalan Bordeaux EL, ®Cibafast N or similar compounds, hindered phenols and derivatives thereof (optionally also as counter-ions X), such as ®Cibafast AO, o-hydroxyphenyl-triazoles or -triazines or other UV absorbers, such as ®Cibafast W or ®Cibafast P or hindered amines (TEMPO or HALS, also as nitroxides or NOR-HALS, optionally also as counter-ions X), and also as cations diimmonium
  • optical recording media for example from US-5 219 707, JP-A-06/199045, JP-A-07/76169, JP-A-07/262604 or JP-A-2000/272241.
  • They may be, for example, salts of the metal complex anions disclosed above with any desired cations, for example the cations disclosed above, or metal complexes, illustrated, for example, by a compound of formula
  • concentrations of additives are, for example, from 0.001 to 1000% by weight, preferably from 1 to 50% by weight, based on the recording medium of formula (I).
  • the optical recording materials according to the invention exhibit excellent spectral properties of the solid amorphous recording layer.
  • the refractive index is extraordinarily high, in some cases even above 2.5.
  • the absorption band is narrow and intense, the absorption band being especially steep on the long-wavelength side.
  • Crystallites are unexpectedly and very advantageously not formed or are formed only to a negligible extent.
  • the reflectivity of the layers in the range of the writing and reading wavelength is very high in the unwritten state.
  • Recording and playback can take place at the same wavelength, therefore advantageously requiring a simple optical system with a single laser source of advantageously from 350 to 500 nm, preferably from 370 to 450 nm.
  • the UV range from 370 to 390 nm, especially approximately 380 nm, or especially at the edge of the visible range of from 390 to 430 nm, more especially approximately 405 ⁇ 5 nm.
  • blue or violet laser diodes such as Nichia GaN 405 nm
  • the marks can be so small and the tracks so narrow that up to about 20 to 25 Gb per recording layer is achievable on a 120 mm disc.
  • UV-VCSELs V ertical- C avity S urface- E mitting Laser
  • the invention therefore relates also to a method of recording or playing back data, wherein the data on an optical recording medium according to the invention are recorded or played back at a wavelength of from 350 to 500 nm.
  • the recording medium is based on the structure of known recording media and is, for example, analogous to those mentioned above. It may be composed, for example, of a transparent substrate, a recording layer comprising at least one of the compounds of formula (I), a reflector layer and a covering layer, the writing and readout being effected through the substrate.
  • Suitable substrates are, for example, glass, minerals, ceramics and thermosetting and thermoplastic plastics.
  • Preferred supports are glass and homo- or co-polymeric plastics.
  • Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins.
  • Special preference is given to polycarbonate substrates which can be produced, for example, by injection-moulding.
  • the substrate can be in pure form or may comprise customary additives, for example UV absorbers or dyes, as proposed e.g. in JP-A-04/167239 as light stabilisation for the recording layer. In the latter case it may be that in the range of the writing wavelength (emission wavelength of the laser) the dye added to the support substrate has no or at most only very low absorption, preferably up to a maximum of about 20% of the laser light
  • the substrate is advantageously transparent over at least a portion of the range from 350 to 500 nm, so that it is permeable to, for example, at least 80 % of the incident light of the writing or readout wavelength.
  • the substrate is advantageously from 10 ⁇ m to 2 mm thick, preferably from 100 to 1200 ⁇ m thick, especially from 600 to 1100 ⁇ m thick, with a preferably spiral guide groove (track) on the coating side, a groove depth of from 10 to 200 nm, preferably from 80 to 150 nm, a groove width of from 100 to 400 nm, preferably from 150 to 250 nm, and a spacing between two turns of from 200 to 600 nm, preferably from 350 to 450 nm.
  • Grooves of different cross-sectional shape are known, for example rectangular, trapezoidal or V-shaped.
  • the guide groove may additionally undergo a small periodic or quasi-periodic lateral deflection (wobble), so that synchronisation of the speed of rotation and the absolute positioning of the reading head (pick-up) are made possible.
  • the same function can be performed by markings between adjacent grooves (pre-pits).
  • the recording medium is applied, for example, by application of a solution by spin-coating, the objective being to produce a layer that is as amorphous as possible, the thickness of which layer is advantageously from 0 to 40 nm, preferably from 1 to 20 nm, especially from 2 to 10 nm, on the surface ("land") and, depending upon the geometry of the groove, advantageously from 20 to 150 nm, preferably from 50 to 120 nm, especially from 60 to 100 nm, in the groove.
  • Reflecting materials suitable for the reflector layer include especially metals, which provide good reflection of the laser radiation used for recording and playback, for example the metals of Main Groups III, IV and V and of the Sub-Groups of the Periodic Table of the Elements.
  • the reflector layer is advantageously from 5 to 200 nm thick, preferably from 10 to 100 nm thick, especially from 40 to 60 nm thick, but reflector layers of greater thickness, for example 1 mm thick or even more, are also possible.
  • Materials suitable for the covering layer include chiefly plastics, which are applied in a thin layer to the reflector layer either directly or with the aid of adhesion promoters. It is advantageous to select mechanically and thermally stable plastics having good surface properties, which can be modified further, for example written on.
  • the plastics may be thermosetting plastics and thermoplastic plastics.
  • Directly applied covering layers are preferably radiation-cured (e.g. using UV radiation) coatings, which are particularly simple and economical to produce. A wide variety of radiation-curable materials are known.
  • radiation-curable monomers and oligomers are acrylates and methacrylates of diols, triols and tetrols, polyimides of aromatic tetracarboxylic acids and aromatic diamines having C 1 -C 4 alkyl groups in at least two ortho-positions of the amino groups, and oligomers with dialkylmaleinimidyl groups, e.g. dimethylmaleinimidyl groups.
  • adhesion promoters are preferably likewise radiation-curable monomers and oligomers.
  • a second substrate comprising a recording and reflector layer, so that the recording medium is playable on both sides.
  • the optical properties of the covering layer, or the covering materials are essentially unimportant per se provided that, where applicable, curing thereof e.g. by UV radiation is achieved.
  • the function of the covering layer is to ensure the mechanical strength of the recording medium as a whole and, if necessary, the mechanical strength of thin reflector layers. If the recording medium is sufficiently robust, for example when a thick reflector layer is present, it is even possible to dispense with the covering layer altogether.
  • the thickness of the covering layer depends upon the thickness of the recording medium as a whole, which should preferably be a maximum of about 2 mm thick.
  • the covering layer is preferably from 10 ⁇ m to 1 mm thick.
  • the recording media according to the invention may also have additional layers, for example interference layers or barrier layers. It is also possible to construct recording media having a plurality of (for example from two to ten) recording layers. The structure and the use of such materials are known to the person skilled in the art. Where present, interference layers are preferably arranged between the recording layer and the reflecting layer and/or between the recording layer and the substrate and consist of a dielectric material, for example as described in EP-A-0 353 393 of TiO 2 , Si 3 N 4 , ZnS or silicone resins.
  • the recording media according to the invention can be produced by processes known per se, it being possible for various methods of coating to be employed depending upon the materials used and their function.
  • Suitable coating methods are, for example, immersion, pouring, brush-coating, blade-application and spin-coating, as well as vapour-deposition methods carried out under a high vacuum.
  • pouring methods solutions in organic solvents are generally employed.
  • solvents care should be taken that the supports used are insensitive to those solvents.
  • Suitable coating methods and solvents are described, for example, in EP-A-0 401 791.
  • the recording layer is applied preferably by the application of a dye solution by spin-coating, solvents that have proved satisfactory being especially alcohols, e.g. 2-methoxyethanol, isopropanol or n-butanol, hydroxyketones, for example diacetone alcohol or 3-hydroxy-3-methyl-2-butanone, hydroxy esters, for example lactic acid methyl ester or isobutyric acid methyl ester, or preferably fluorinated alcohols, for example 2,2,2-trifluoroethanol or 2,2,3,3-tetrafluoro-1-propanol, and mixtures thereof.
  • solvents that have proved satisfactory being especially alcohols, e.g. 2-methoxyethanol, isopropanol or n-butanol, hydroxyketones, for example diacetone alcohol or 3-hydroxy-3-methyl-2-butanone, hydroxy esters, for example lactic acid methyl ester or isobutyric acid methyl ester, or preferably fluorinated alcohols, for example 2,
  • the application of the metallic reflector layer is preferably effected by sputtering or by vapour-deposition in vacuo .
  • Such techniques are known and are described in specialist literature (e.g. J.L. Vossen and W. Kem, "Thin Film Processes", Academic Press, 1978).
  • the operation can advantageously be carried out continuously and achieves good reflectivity and a high degree of adhesiveness of the metallic reflector layer.
  • Recording is carried out in accordance with known methods by writing pits (marks) of fixed or variable length by means of a modulated, focussed laser beam guided at a constant or variable speed over the surface of the recording layer.
  • Readout of information is carried out according to methods known per se by registering the change in reflection using laser radiation, for example as described in "CD-Player und R-DAT Recorder” (Claus Biaesch-Wiepke, Vogel Buchverlag, Würzburg 1992). The person skilled in the art will be familiar with the requirements.
  • the information-containing medium according to the invention is especially an optical information material of the WORM type. It can be used, for example, analogously to CD-R ( c ompact d isc - r ecordable) or DVD-R ( d igital v ideo disc - r ecordable) in computers, and also as storage material for identification and security cards or for the production of diffractive optical elements, for example holograms.
  • the compounds of formula (I) according to the invention also meet the increased demands of an inverse layer structure surprisingly well. Preference is therefore given to an inverse layer structure having the layer sequence substrate, reflector layer, recording layer and covering layer.
  • the recording layer is therefore located between the reflector layer and the covering layer.
  • a thin covering layer approximately from 50 to 400 ⁇ m in thickness is especially advantageous (typically 100 ⁇ m at a numerical aperture of 0.85).
  • the recording and reflector layers in an inverse layer structure have in principle the same functions as indicated above. As with the groove geometry, they therefore usually have dimensions within the ranges indicated above.
  • the inverse layer structure requires particularly high standards, which the compounds used according to the invention fulfil astonishingly well, for example when the recording layer is applied to the metallic reflector layer and especially when a covering layer is applied to the recording layer, the covering layer being required to provide the recording layer with adequate protection against rubbing, photooxidation, fingerprints, moisture and other environmental effects and advantageously having a thickness in the range of from 0.01 to 0.5 mm, preferably in the range of from 0.05 to 0.2 mm, especially in the range of from 0.08 to 0.13 mm.
  • the covering layer preferably consists of a material that exhibits a transmission of 80% or above at the writing or readout wavelength of the laser.
  • Suitable materials for the covering layer include, for example, those materials mentioned above, but especially polycarbonate (such as Pure Ace® or Panlite®, Teijin Ltd), cellulose triacetate (such as Fujitac®, Fuji Photo Film) or polyethylene terephthalate (such as Lumirror®, Toray Industry), special preference being given to polycarbonate.
  • polycarbonate such as Pure Ace® or Panlite®, Teijin Ltd
  • cellulose triacetate such as Fujitac®, Fuji Photo Film
  • polyethylene terephthalate such as Lumirror®, Toray Industry
  • radiation-cured coatings such as those already described above, are advantageous, for example SD 347TM (Dainippon Ink).
  • the covering layer can be applied directly to the solid recording layer by means of a suitable adhesion promoter.
  • an additional, thin separating layer of a metallic, crosslinked organometallic or preferably dielectric inorganic material for example in a thickness of from 0.001 to 10 ⁇ m, preferably from 0.005 to 1 ⁇ m, especially from 0.01 to 0.1 ⁇ m, for example from 0.05 to 0.08 ⁇ m in the case of dielectric separating layers and from 0.01 to 0.03 ⁇ m in the case of metallic separating layers.
  • such coatings can be applied, for example, in the same thickness also between the support material and the metallic reflector layer or between the metallic reflector layer and the optical recording layer. This may be advantageous in certain cases, for example when a silver reflector is used in combination with sulfur-containing additives in the recording layer.
  • an additional, thin separating layer of a metallic, crosslinked organometallic or dielectric inorganic material for example in a thickness of from 0.001 to 10 ⁇ m, preferably from 0.005 to 1 ⁇ m, especially from 0.01 to 0.1 ⁇ m.
  • metallic separating layers should advantageously be a maximum of 0.03 ⁇ m thick.
  • the invention therefore relates also to compounds of formula (I), with the exception of the already known compounds of formula M 2 (Z 1 ) 2 , wherein:
  • G 1 and G 2 are the preferred heterocydes disclosed above and at the same time or independently thereof M 1 is a preferred transition metal.
  • a 3 in G 1 and G 2 can be especially N(R 12 ), O, S or, especially in formula (III), C(C 1 -C 5 alkyl) 2 -
  • mixtures by mixed synthesis instead of preparing mixtures by mixing together the components, it is favourably possible to prepare mixtures by mixed synthesis, the metals being added in any desired order in succession or preferably simultaneously to a pre-prepared mixture of the ligands, or conversely the ligands being added in any desired order in succession or preferably all of them simultaneously to a pre-prepared mixture of the metals.
  • the mixtures prepared by mixed synthesis generally have somewhat better solubility than physical mixtures, possibly because of their asymmetric components.
  • the optical recording media according to the invention may also comprise other chromophores, preferably metal-free chromophores.
  • Other chromophores may, if desired, be added in an amount of from 1 to 200 % by weight, based on the total of the compounds of formula (I).
  • the amount of other chromophores is preferably from 5 to 100 % by weight, especially from 10 to 50 % by weight, based on the total of the compounds of formula (I).
  • Chromophores can be dyes or UV absorbers, preferably having an absorption maximum of from 350 to 400 nm or at from 600 to 700 nm, for example around 380 or 630 nm.
  • Especially preferred additional metal-free chromophores are cyanines, azacyanines, merocyanines and oxonols and also rhodamines, for example those disclosed in WO 04/006878, WO 02/082438 or EP-A-1 083 555, and also wherein R 40 is C 1 -C 24 alkyl or C 2 -C 24 alkenyl, each of which can be unsubstituted or substituted, and R 41 is any substituent R 40 may be, for example, methyl, ethyl, vinyl, allyl, isopropyl, n-butyl, 2-isopropyloxy-ethyl, n-pentyl, 3-methyl-butyl, 3,3-dimethylbutyl, 2-ethyl-hexyl, 2-cyano-ethyl, furan-2-yl-methyl or 2-hydroxy-methyl; R 41 is, for example, C 6 -C 10 aryl, C 1 -
  • Example 1 1.0 g of the compound of formula is applied in the form of a dichloromethane solution to glass. The solid layer is irradiated for 90 hours with xenon light according to ISO-105-B02 (Atlas Ci-35 Weather-O-meter, 15 kJ/cm 2 ). The light stability is excellent (see Example 7).
  • Example 2 On the solid layer according to Example 1, marks are written into the recording layer using a pulsed dye laser (15 ns pulse length) at a wavelength of 405 nm at an energy density of 0.8 kJ/m 2 . The written sites exhibit a resulting change in reflectivity.
  • Example 3 0.5 g of the compound according to Example 1 is dissolved in 99.5 g of dioxane and applied by means of spin-coating to a silicon wafer. The colourless solid layer is measured using a spectral ellipsometer (Sopra). At a wavelength of 405 nm a refractive index of 2.52 is determined.
  • Example 4 1.0 g of the compound of formula is dissolved in 99 g of methylcyclohexane and filtered through a 0.2 ⁇ m Teflon filter. The dye solution is then applied by rotation at 250 rev/min to a 1.2 mm thick, flat polycarbonate plate (diameter 120 mm). The rotational speed is then increased to 1200 rev/min, so that the excess solution is spun off, and a uniform solid layer is formed. After drying, the solid layer has an absorption of 0.61 at 382 nm. Using an optical measuring system (ETA-RT, STEAG ETA-Optik), the layer thickness and the complex refractive index are determined. At 405 nm the dye layer has a layer thickness of 56 nm, a refractive index n of 1.95 and an extinction coefficient k of 0.090.
  • ETA-RT ETA-RT, STEAG ETA-Optik
  • Example 6 1.0 g of the complex according to Example 5 is dissolved in 99 g of 2,2,3,3-tetrafluoro-1-propanol and filtered through a 0.2 ⁇ m Teflon filter. The dye solution is then applied by rotation at 250 rev/min to a 1.2 mm thick, flat polycarbonate plate (diameter 120 mm); the rotational speed is then increased to 1500 rev/min, so that the excess solution is spun off and a uniform solid layer is formed. After drying, the solid layer has an absorption of 0.35 at 356 nm. Using an optical measuring system (ETA-RT, STEAG ETA-Optik), the layer thickness and the complex refractive index are determined. At 405 nm the dye layer has a layer thickness of 18 nm, a refractive index n of 2.25 and an extinction coefficient k of 0.031.
  • ETA-RT ETA-RT, STEAG ETA-Optik
  • Examples 7 - 38 The procedure is analogous to Example 6, but instead of the complex of Example 5 the following ligands and metal cations are used: Metal Ligand(2 ⁇ ) ⁇ max [nm] Solvent n k Cu 2+ 370 CH 3 CN (+HCl) 2.52 0.47 Cu 2+ 383 CH 2 Cl 2 2.30 0.185 Ni 2+ 370 CH 2 Cl 2 , 2.23 0.160 Cu 2+ 390 CH 2 Cl 2 2.22 0.266 Cu 2+ 377 CH 2 Cl 2 2.21 0.244 Co 2 + 370 CH 2 Cl 2 2.20 0.137 Co 2+ 376 CH 2 Cl 2 2.19 0.179 Ni 2+ 361 CH 2 Cl 2 2.17 0.108 Co 2+ 370 CH 2 Cl 2 2.08 0.158 Ni 2+ 361 CH 2 Cl 2 2.07 0.097 Cu 2+ 384 CH 2 Cl 2 2.00 0.092 Co 2+ 351 CH 2 Cl 2 1.98 0.100 Co 2+ 370 CH 2 Cl 2 1.94 0.083 Ni 2 + 350 CH 2 Cl 2 1.93 0.083 Co 2+ 367
  • Examples 39 - 62 The procedure is analogous to Example 6, but instead of the complex of Example 5 the mixtures M1 to M24 are used.
  • Examples 63 - 86 The procedure is analogous to Example 6, but instead of the complex of Example 5 there are used mixtures having the same proportions of metal and ligand as mixtures M1 to M24 but the complexes are prepared by mixed synthesis (variant of the simultaneous addition of the metal mixture to the ligand mixture). The results are similar to those of Examples 39 - 62, but have surprisingly better solubility and solution stability.
  • Examples 87 - 94 The procedure is analogous to Example 6, but instead of the complex of Example 5 there are used the following mixtures of compounds of formula (I) with cyanines and merocyanines:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP04713552A 2003-03-03 2004-02-23 Optical recording materials having high storage density Expired - Lifetime EP1599878B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH3312003 2003-03-03
CH3312003 2003-03-03
PCT/EP2004/050185 WO2004079732A1 (en) 2003-03-03 2004-02-23 Optical recording materials having high storage density

Publications (2)

Publication Number Publication Date
EP1599878A1 EP1599878A1 (en) 2005-11-30
EP1599878B1 true EP1599878B1 (en) 2006-06-07

Family

ID=32932301

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04713552A Expired - Lifetime EP1599878B1 (en) 2003-03-03 2004-02-23 Optical recording materials having high storage density

Country Status (10)

Country Link
US (1) US20060159882A1 (https=)
EP (1) EP1599878B1 (https=)
JP (1) JP2006523553A (https=)
KR (1) KR20050115265A (https=)
CN (1) CN1757066A (https=)
AT (1) ATE329351T1 (https=)
DE (1) DE602004001135T2 (https=)
RU (1) RU2005130516A (https=)
TW (1) TW200428381A (https=)
WO (1) WO2004079732A1 (https=)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002082438A2 (en) * 2001-03-21 2002-10-17 Ciba Specialty Chemicals Holding Inc. Optical recording materials having high storage density
DE602004010451T2 (de) * 2003-04-15 2008-11-20 Ricoh Co., Ltd. Einmal beschreibbarer, mehrmals lesbarer optischer Datenträger und Verfahren zum Beschreiben und Lesen des Datenträgers
EP1719126A1 (en) * 2004-02-23 2006-11-08 CIBA SPECIALTY CHEMICALS HOLDING INC. Patent Departement Optical recording materials having high storage density
JP2008509029A (ja) * 2004-08-10 2008-03-27 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド 高い記憶密度を有する光記録材料
EP1710793A1 (de) * 2005-04-05 2006-10-11 Ciba SC Holding AG Metallchelate und ihre Verwendung in optischen Aufzeichnungsmedien mit hoher Speicherkapazität
CA2786425C (en) * 2010-01-19 2016-12-20 Sumitomo Seika Chemicals Co., Ltd. Composition for ultraviolet absorbent substance and ultraviolet absorbent substance comprising same
JP5400717B2 (ja) * 2010-06-30 2014-01-29 住友精化株式会社 合成樹脂用安定化剤、該安定化剤を含有する合成樹脂組成物および樹脂部材

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1932894A1 (de) * 1969-06-28 1971-01-28 Basf Ag Metallkomplexfarbstoffe
AU5561198A (en) * 1996-12-20 1998-07-17 Ciba Specialty Chemicals Holding Inc. Complex polymethine dyes and their use
US6162520A (en) * 1997-09-17 2000-12-19 Mitsui Chemicals, Inc. Optical recording medium and dipyrromethene metal chelate compound for use therein
US6376664B1 (en) * 1999-03-17 2002-04-23 The Ohio State University Cyclic bis-benzimidazole ligands and metal complexes thereof
US6479123B2 (en) * 2000-02-28 2002-11-12 Mitsui Chemicals, Inc. Dipyrromethene-metal chelate compound and optical recording medium using thereof
WO2002082438A2 (en) * 2001-03-21 2002-10-17 Ciba Specialty Chemicals Holding Inc. Optical recording materials having high storage density
EP1719126A1 (en) * 2004-02-23 2006-11-08 CIBA SPECIALTY CHEMICALS HOLDING INC. Patent Departement Optical recording materials having high storage density

Also Published As

Publication number Publication date
US20060159882A1 (en) 2006-07-20
WO2004079732A1 (en) 2004-09-16
HK1082980A1 (en) 2006-06-23
DE602004001135T2 (de) 2007-04-12
ATE329351T1 (de) 2006-06-15
KR20050115265A (ko) 2005-12-07
JP2006523553A (ja) 2006-10-19
EP1599878A1 (en) 2005-11-30
CN1757066A (zh) 2006-04-05
DE602004001135D1 (de) 2006-07-20
RU2005130516A (ru) 2006-06-27
TW200428381A (en) 2004-12-16

Similar Documents

Publication Publication Date Title
JP2007290401A (ja) 高い記憶密度を有する光学記録材料
JP2005525956A (ja) 五環式キサンチリウム染料を含む光学記憶媒体
EP1599878B1 (en) Optical recording materials having high storage density
CN100519530C (zh) 高储存密度光学记录材料
US20080130474A1 (en) Optical Recording Materials Having High Stroage Density
JP2005525957A (ja) 高性能光記憶媒体
US20070184232A1 (en) Optical recording materials having high storage density
HK1082980B (en) Optical recording materials having high storage density
JP2006526516A (ja) 大容量光学記憶媒体
US20070172624A1 (en) Optical recording materials writable using blue lasers
US20080095967A1 (en) Optical Recording Materials Having High Storage Density
WO2005081239A1 (en) Optical recording materials having high storage density

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050804

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1082980

Country of ref document: HK

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602004001135

Country of ref document: DE

Date of ref document: 20060720

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060907

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060918

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061107

REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1082980

Country of ref document: HK

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20061212

Year of fee payment: 4

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20061219

Year of fee payment: 4

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20070110

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20070228

Year of fee payment: 4

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070308

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060908

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080229

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080229

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20080901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080901

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080223

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080902

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061208

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080223

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070228

Year of fee payment: 4